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Humidity Sensitivity of Hydration of Expansive Agent and Its Expansive Efficiency in Ultra-High Performance Concrete
Humidity Sensitivity of Hydration of Expansive Agent and Its Expansive Efficiency in Ultra-High Performance Concrete
Article
Humidity Sensitivity of Hydration of Expansive Agent and Its
Expansive Efficiency in Ultra-High Performance Concrete
Yujiang Wang 1,2, *, Qian Tian 2 , Hua Li 1,2 and Yang Wang 2
1 Jiangsu Key Laboratory of Construction Materials, College of Materials Science and Engineering,
Southeast University, Nanjing 211189, China; lihua@cnjsjk.cn
2 State Key Laboratory of High Performance Civil Engineering Materials, Jiangsu Sobute New
Materials Co., Ltd., Nanjing 211103, China; tianqian@cnjsjk.cn (Q.T.); wangyang@cnjsjk.cn (Y.W.)
* Correspondence: wangyujiang@cnjsjk.cn
Abstract: Ultra-high performance concrete (UHPC) has a potential cracking risk due to its large
autogenous shrinkage. The use of an expansive agent is an effective approach to reduce autogenous
shrinkage of UHPC. However, different kinds of expansive agents show different expansive efficiency
in UHPC. To study the cause for the difference in expansive efficiency, this study selected three
expansive agents, namely highly reactive MgO-based, medium reactive MgO-based, and CaO-based
expansive agents, and carried out the following experiments: autogenous shrinkage, hydration
heat, hydration process of expansive agent under different relative humidity (RH), and micrographs.
The results showed that the CaO-based expansive agent has high hydration activity at RH of more
than 44.0%, while the hydration activity of two kinds of MgO-based expansive agents, especially a
medium reactive MgO-based expansive agent, decreases significantly when RH drops below 80%.
Meanwhile, the CaO-based expansive agent had higher expansive efficiency in UHPC than the MgO-
based expansive agent. This study suggested that the CaO-based expansive agent is more suitable for
Citation: Wang, Y.; Tian, Q.; Li, H.; compensating autogenous shrinkage of UHPC due to its low humidity sensitivity compared to the
Wang, Y. Humidity Sensitivity of MgO-based expansive agent.
Hydration of Expansive Agent and
Its Expansive Efficiency in Ultra-High Keywords: ultra-high performance concrete; autogenous shrinkage; hydration; CaO-based expansive
Performance Concrete. Crystals 2022, agent; MgO-based expansive agent
12, 195. https://doi.org/10.3390/
cryst12020195
Figure1.1.Clinker
Figure Clinkerof
ofCaO-based
CaO-basedexpansive
expansiveagent.
agent.
Themix
The mixproportions
proportionsof ofUHPC
UHPCstudied
studiedareareshown
shownin inTable
Table2.2.All
Allconcrete
concretemixtures
mixtures
haveaa0.17
have 0.17w/b,
w/b, which
which is widely
widely used
used in
in concrete
concrete engineering.
engineering.UHPC
UHPCisismixed
mixedwith
withcoarse
coarse
aggregatetotoreduce
aggregate reduceitsitsautogenous
autogenous shrinkage.
shrinkage. The
The dosage
dosage of of MgO-based
MgO-based expansive
expansive agent
agent is
is 4%
4% andand
6%6% of the
of the mass
mass of cementitious
of cementitious material,
material, while
while the the dosage
dosage of CaO-based
of CaO-based expan-
expansive
sive agent
agent is 1%, is
2%1%,and2%3%. and 3%. A commercial
A commercial powderpowder polycarboxylate-based
polycarboxylate-based superplasti-
superplasticizer was
used
cizerfor
was allused
mixtures.
for allThe dosage The
mixtures. of the superplasticizer
dosage is 1.1% of theismass
of the superplasticizer 1.1%ofof
cementitious
the mass of
materials.
cementitiousIt should be noted
materials. that fiber
It should is notthat
be noted considered
fiber is in
notUHPC mix proportion,
considered in order
in UHPC mix pro-
to avoid the
portion, influence
in order of fiber
to avoid theon autogenous
influence shrinkage.
of fiber on autogenous shrinkage.
3
Table2.2.Mix
Table Mixproportions
proportionsofofUHPC
UHPC(kg/m
(kg/m3).
Silica
Silica Fine
Fine Coarse
Coarse
Water
Water Cement
Cement H-MEA
H-MEA M-MEA
M-MEA CA Superplasticizer
CA Superplasticizer
Fume
Fume Aggregate
Aggregate Aggregate
Aggregate
Control
Control 201
201 1125
1125 59
59 592 480
480 // // // 13
13
H-MEA-4%
H-MEA-4% 201
201 1080
1080 57
57 592
592 480
480 47
47 // // 13
13
H-MEA-6% 201 1057 56 592 480 71 / / 13
H-MEA-6% 201 1057 56 592 480 71 / / 13
M-MEA-4% 201 1080 57 592 480 / 47 / 13
M-MEA-4%
M-MEA-6% 201
201 1080
1057 57
56 592
592 480
480 // 47
71 // 13
13
M-MEA-6%
CA-1% 201
201 1057
1114 56
59 592
592 480
480 // 71
/ 12/ 13
13
CA-2%
CA-1% 201
201 1102
1114 58
59 592 480
480 // // 24
12 13
13
CA-3%
CA-2% 201
201 1091
1102 57
58 592
592 480
480 // // 36
24 13
13
CA-3% 201 1091 57 592 480 / / 36 13
2.2. Autogenous Shrinkage
2.2. Autogenous
Figure 2 showsShrinkage
the apparatus for measuring autogenous shrinkage of UHPC. Concrete
mixture was2first
Figure showscastthe
intoapparatus
a cylindrical PVC tube (Ø
for measuring 100 mm ×
autogenous 500 mm)ofpre-sealed
shrinkage UHPC. Con- by
epoxy resin at the
crete mixture wasbottom. Then,
first cast into the concrete surface
a cylindrical was(Ø
PVC tube covered
100 mm with plastic
× 500 mm)film. When
pre-sealed
the
by concrete
epoxy resinlosesatfluidity, a metal
the bottom. headthe
Then, was embedded
concrete in the
surface was surface
coveredconcrete. After that,
with plastic film.
the
When the concrete loses fluidity, a metal head was embedded in the surface concrete.The
surface of the specimen is covered with paraffin to prevent water evaporation. Af-
vertical
ter that,autogenous
the surface of deformation
the specimen wasismeasured by aparaffin
covered with dial gauge at different
to prevent water ages. The test
evaporation.
zero
The point is the
vertical initial setting
autogenous of concrete,
deformation waswhich was determined
measured by penetration
by a dial gauge at differentresistance
ages. The
according
test zero point is the initial setting of concrete, which was determined 20.0
to ASTM C403 [28]. The ambient temperature of the test was ± 1.0 ◦ C. re-
by penetration
sistance according to ASTM C403 [28]. The ambient temperature of the test was 20.0 ± 1.0
2.3. Internal Relative Humidity
°C.
Internal RH of UHPC was measured using a humidity sensor (HC2-S, Rotronic,
Bassersdorf, Switzerland) with an accuracy of 0.8% RH. Test methods referred to liter-
ature [13], and the test procedure was as follows: UHPC mixture was first placed in a
sealed plastic bottle. At the age of 10 h, the UHPC sample was crushed into pieces. Then,
2.36–4.74 mm pieces were chosen by sieves and inserted into a metal chamber for RH
measurement. In addition, the metal chamber was placed in a water bath to keep the
temperature of 20 ± 0.1 ◦ C.
Dial
gauge
paraffin
wax
Metal
head
PVC
tube
Crystals 2022,
Crystals 12, x195
2022, 12, FOR PEER REVIEW Concrete 44 of
of 10
10
Epoxy
resin
Dial
Figure
gauge 2. Apparatus for autogenous shrinkage measurement.
paraffin
wax
2.3. Internal
Metal Relative Humidity
head
PVC
Internal RH of UHPC was measured using a humidity sensor (HC2-S, Rotronic,
tube
Bassersdorf, Switzerland) with an accuracy of 0.8% RH. Test methods referred to literature
Concrete
[13], and the test procedure was as follows: UHPC mixture was first placed in a sealed
plastic bottle. At the age of 10 h, the UHPC sample was crushed into pieces. Then, 2.36–
Epoxy
resin
4.74 mm pieces were chosen by sieves and inserted into a metal chamber for RH measure-
ment. In addition, the metal chamber was placed in a water bath to keep the temperature
Figure
of 20 ±2.
Figure Apparatus
2.0.1 °C.
Apparatus for
for autogenous
autogenous shrinkage
shrinkage measurement.
measurement.
2.3.
2.4.Internal
2.4. Hydration
Hydration Relative Humidity
ofofExpansive
Expansive Agent
Agentunder
underDifferent
DifferentRH RH
As
Internal ◦ C isRotronic,
As shown in Figure 3, the relative humidityofofa93%,
shown RH in Figure
of UHPC 3, thewasrelative humidity
measured using 93%, 81%
humidity81%andand 44%44%atat
sensor 20
(HC2-S,
20 °C isachieved
achieved
through
Bassersdorf, three saturated
Switzerland) salt solutions
with an of KNO
accuracy of 3 , (NH4)
0.8% RH.2 SOTest
4 , and
through three saturated salt solutions of KNO3, (NH4)2SO4, and K2CO3·2H2O, respectively. K
methods
2 CO · 2H
referred
3 2 O, respectively.
to literature
Furthermore,
[13], and the test
Furthermore, the
thehydration
hydrationof
procedure ofexpansive
was agent
as follows:
expansive UHPC
agent atat60% isisstudied
mixture
60% wasin
studied aadrying
first
in placedroom,
drying which
in a sealed
room, which
isisaastandard
plastic bottle. test
At environment
the age of 10 h,for measuring
the UHPC the
sample drying
was shrinkage
crushed
standard test environment for measuring the drying shrinkage of concrete in China. intoof concrete
pieces. in
Then, China.
2.36–
The
4.74
Themm thickness
pieces of
thickness of expansive
were chosen by
expansive agent
agent powder
sieves is
and inserted
powder less
is less than than
into2amm. 2 mm.
metalAfter After
chamber reaching
reachingfor RH a certain
measure-
a certain age,
age,
ment. the
In expansive
addition, agent
the metal was immersed
chamber was in alcohol
placed in for
a 1
water h to
the expansive agent was immersed in alcohol for 1 h to terminate hydration. After immer- terminate
bath to keep hydration.
the After
temperature
immersion
of 20 ±was0.1 °C.was concluded, the sample was vacuum dried for 2 h and then dried for 1 d at
sion concluded, the sample was vacuum dried for 2 h and then dried for 1 d at 105
105 ◦ C. Finally, the weight loss of the sample during 105 ◦ C to 1050 ◦ C was measured by a
°C. Finally, the weight loss of the sample during 105 °C to 1050 °C was measured by a
differential
2.4. Hydration scanning calorimetry
of Expansive Agent under(SDTQ600,
DifferentTARH Instruments, New Castle, DE, USA). The
differential scanning calorimetry (SDTQ600, TA Instruments, New Castle, DE, USA). The
hydration
As showndegree of the
in Figure expansive agent was calculated
of 93%, according to Equation
20 °C is(1).
hydration degree of the 3, the relative
expansive humidity
agent was calculated 81% and 44%
according to at
Equation achieved
(1).
through three saturated salt solutions of KNO 3, (NH4)2SO4, and K2CO3·2H2O, respectively.
L E𝐿· M∙E𝑀
Furthermore, the hydration of expansive α= 𝛼=
agent at 60% is studied in a drying room, which (1)
(1)
M𝑀 H ·C∙ 𝐶
is a standard test environment for measuring the drying shrinkage of concrete in China.
where
where
The ααisis the
thickness theofhydration
expansivedegreeagent of of CaO
CaOor
powder is MgO,
or MgO,
less LL
than is2is
EE mass
mass
mm. loss ofreaching
loss
After thethe
of sample
sample during
a certain 105
during
age,
◦to
°Cexpansive
C1050 ◦M
°C,agent iswas
105
the to 1050 C,EM Ethe molar
is the molar
immersed massinof
mass CaO
of CaO
alcohol or
for MgO,
or h toM
1MgO, H is
M the
H is
terminate themolar
molarmass
hydration. ofofHH
massAfter 2O, and
2 O, andC
immer-
Cisiscontent
sion content ofofCaO
was concluded, CaOororthe MgO
MgO ininexpansive
sample expansive
was vacuumagent.
agent. dried for 2 h and then dried for 1 d at 105
°C. Finally, the weight loss of the sample during 105 °C to 1050 °C was measured by a
differential scanning calorimetry (SDTQ600, TA Instruments, New Castle, DE, USA). The
hydration degree of the expansive agent was calculated according to Equation (1).
Expansive
agent 𝐿 ∙𝑀
𝛼= (1)
𝑀 ∙𝐶
saturated salt
where α is the hydration
solutions degree of CaO or MgO, LE is mass loss of the sample during 105
°C to 1050 °C, ME is the molar mass of CaO or MgO, MH is the molar mass of H2O, and C
Figure3.3.Apparatus
contentApparatus
Figure
is forproviding
of CaO orforMgO providingaaconstant
constantRH.
in expansive RH.
agent.
2.5.Isothermal
2.5. IsothermalCalorimetry
CalorimetryMeasurements
Measurements
Hydrationprocess
Hydration processof ofthe
thepaste
pastewas
wasdetermined
determinedby byisothermal
isothermalcalorimeter
calorimeter(TAM
(TAMAirAir
Isothermal
IsothermalCalorimeter,
Expansive TA
Calorimeter, TAInstrument).
Instrument).The
Themixing
mixingproportions
proportionsofofpastes
pasteswere
werederived
derived
agent
from
fromtheir
theircorresponding
correspondingconcrete mixtures
concrete (Table
mixtures 2) by
(Table subtracting
2) by the the
subtracting aggregate fraction.
aggregate frac-
tion.
2.6. Micrographs saturated salt
solutions
Micrographs of the expansive agent before and after hydration were examined by
Figure 3. Apparatus
scanning for providing(SEM,
electron microscope a constant
FEI).RH.
3. Results
2.5. andCalorimetry
Isothermal DiscussionMeasurements
3.1. Effect of Expansive
Hydration processAgent onpaste
of the Autogenous Shrinkage of
was determined byUHPC
isothermal calorimeter (TAM Air
Isothermal
FigureCalorimeter, TA Instrument).
4 shows the autogenous The mixing
shrinkage UHPCproportions of pastes
with and without were derived
expansive agent.
The results
from show that 28 concrete
their corresponding d autogenous shrinkage
mixtures (Table 2)ofby
UHPC without
subtracting theexpansive
aggregateagent
frac-
exceeds 600 µε, although the coarse aggregate at a volume ratio of 0.17 is added to the
tion.
scanning electron microscope (SEM, FEI).
0 0 100
Autogenou deformation (με)
Control
Figure
Figure 4.
4. Autogenous
Autogenousshrinkage
shrinkageofofUHPC
UHPCwith
withand without
and expansive
without agent:
expansive (a) (a)
agent: highly reactive
highly reactive
MgO-based
MgO-based expansive
expansive agent;
agent; (b)
(b) medium
medium reactive
reactive MgO-based
MgO-based expansive
expansive agent;
agent; and
and (c)
(c)CaO-based
CaO-based
expansive
expansive agent.
agent.
Figure
Figure 4a 4a shows
shows the the expansive
expansive efficiency
efficiency of
of the
thehighly
highlyreactive
reactiveMgO-based
MgO-based expansive
expansive
agent.
agent. TheTheresults
resultsshow
showthatthat4% 4%and
and6%6% highly
highlyreactive
reactive MgO-based
MgO-based expansive
expansive agents re-
agents
duce
reduce thethe
autogenous
autogenous shrinkage
shrinkage byby
20.5%
20.5%andand23.2%
23.2%atat7 7d,d,respectively,
respectively,and and 18.6%
18.6% and
and
23.9%
23.9% atat 28
28 d,
d, respectively.
respectively. TheThe results
results further
further indicate
indicate that
that expansive
expansive efficiency
efficiency ofof highly
highly
reactive
reactive MgO-based
MgO-basedexpansive
expansiveagentagentisisvery
veryclose
closeatat7 7d d
andand 2828d.d.Figure
Figure 4b4bshows
shows that at
that
28 d, d,
at 28 6%6% medium
medium reactive
reactiveMgO-based
MgO-basedexpansive
expansiveagentagentonly onlyreduces
reduces the the autogenous
autogenous
shrinkage
shrinkage by byabout
about5.9%,
5.9%,and
and there is no
there significant
is no significantdifference
difference in expansive
in expansive efficiency be-
efficiency
between
tween 4%4% and and
6%6% dosage
dosage of medium
of medium reactive
reactive MgO-based
MgO-based expansive
expansive agent.
agent.
As shown
As shown in in Figure
Figure 4c,4c, the CaO-based
CaO-based expansive
expansive agent agent shows
shows aa higher
higher expansive
expansive
efficiency compared
efficiency compared with with the MgO-based expansive agent. 1%, 2%
MgO-based expansive agent. 1%, 2% and 3% CaO-based and 3% CaO-based
expansive agent
expansive agent can
can reduce
reduce the
the autogenous
autogenousshrinkage
shrinkageby by16.4%,
16.4%,45.8%
45.8%and and70.0%,
70.0%,respec-
respec-
tively. In
tively. In addition,
addition, thethe results
results show
show that
that the
the CaO-based
CaO-based expansive
expansive agentagent shows
shows an an obvious
obvious
expansion before
expansion before 11 d, d, especially
especially in the UHPC with 3.0% CaO-based expansive agent. It It
should be noted that
should that in
inthis
thisstudy,
study,CaO-based
CaO-basedexpansive
expansive agent
agent shows
shows remarkably
remarkably expansive
expan-
efficiency
sive at a low
efficiency at amass dosage
low mass of 1–3%,
dosage while while
of 1–3%, in studies of ShenofetShen
in studies al. [10], the
et al. mass
[10], thedosage
mass
of CaO-based expansive agent reached 15%. This difference
dosage of CaO-based expansive agent reached 15%. This difference in the dosage in the dosage may mainly
may
due to the
mainly duefact thatfact
to the the that
CaO-based expansive
the CaO-based agent used
expansive agent in this
usedstudy
in thisis grinded
study is from the
grinded
clinker,
from thewhile the while
clinker, commercial CaO-basedCaO-based
the commercial expansive agent
expansivegenerally
agent add other components.
generally add other
components.
3.2. Internal RH of UHPC
Figure RH
3.2. Internal 5 shows the development of internal RH of the UHPC without expansive agent
of UHPC
(Control). At the ages of 3, 7, and 28 d, internal RH of the UHPC is 89.7%, 77.0% and 67.1%,
Figure 5 shows the development of internal RH of the UHPC without expansive
respectively. The test results are consistent with the results of Loukili et al. [24]. In addition,
agent (Control). At the ages of 3, 7, and 28 d, internal RH of the UHPC is 89.7%, 77.0% and
the development process of internal RH is similar to that of the autogenous shrinkage. They
67.1%, respectively. The test results are consistent with the results of Loukili et al. [24]. In
all show a rapidly change process in the first few days. Furthermore, the results imply
addition, the development process of internal RH is similar to that of the autogenous
that the expansive agent should have a high hydration activity in the rapidly decreasing
process of the RH, especially when the RH is below 80%, in order to decrease autogenous
shrinkage of UHPC effectively.
shrinkage. They all show a rapidly change process in the first few days. Furthermore, the
results imply that the expansive agent should have a high hydration activity in the rapidly
shrinkage. They all show a rapidly change process in the first few days. Furthermore, the
decreasing process of the RH, especially when the RH is below 80%, in order to decrease
results imply that the expansive agent should have a high hydration activity in the rapidly
autogenous shrinkage of UHPC effectively.
Crystals 2022, 12, 195 decreasing process of the RH, especially when the RH is below 80%, in order to decrease6 of 10
autogenous shrinkage of UHPC effectively.
95
RH=93%
10080 10080 10080
Hydration degree (%)
Hydration degree (%)
RH=81%
RH=60%
8060 8060 RH=44%
RH=93% 8060
Hydration degree (%)
Hydration degree (%)
RH=81%
RH=93%
RH=60%
RH=81%
6040 6040 RH=44% 6040
RH=60%
RH=44%
RH=93%
4020 4020 4020 RH=81%
RH=93% RH=81% RH=60%
RH=60% RH=44% RH=44%
20 0 20 0 20 0
0 5 10RH=93%
15 RH=81%
20 25 30 0 5 10 15 20 25 30 0 5 10 15 20 25 30
RH=60% RH=44%
0 Age (d) 0 Age (d) 0 Age (d)
0 5 10 15 20 25 30 0 5 10 15 20 25 30 0 5 10 15 20 25 30
Age (d) Age (d) Age (d)
humidity sensitivity of the hydration, medium reactive MgO-based expansive agent can
hardly hydrate with water in UHPC, especially when the RH is below 80%, and resulting
agent
in can hardly
a negligible hydrate with
difference water in UHPC,
in expansive especially
efficiency between when the RH
4% and 6%isdosage.
below 80%, and
Further-
resulting
more, the in a negligibleofdifference
effectiveness in expansive
highly reactive efficiency
MgO-based between
expansive 4% in
agent and 6% dosage.
UHPC is be-
Furthermore,
tween CaO-basedthe effectiveness
and mediumof highly MgO-based
reactive reactive MgO-based expansive
expansive agent. agent in UHPC is
between CaO-based and medium reactive MgO-based expansive agent.
3.4. Hydration Heat of the Paste
3.4. Hydration Heat of the Paste
The hydration heat of the paste is shown in Figure 7. The results show that 7 d hy-
Theheat
dration hydration heat of
of the paste withtheexpansive
paste is shown
agent isinhigher
Figurethan
7. The
thatresults
of the show
paste that 7d
without
hydration heat of the paste with expansive agent is higher than that of the paste
expansive agent. The effect of expansive agent on the hydration heat is mainly due to the without
expansive
higher agent.heat
hydration Theofeffect
CaO ofandexpansive agent on agent
MgO in expansive the hydration
than that heat is mainly
of cement. due to
The results
the higher hydration heat of CaO and MgO in expansive agent than that of cement.
indicate that hydration reaction of the three kind of expansive agents occurs in the first The7
results indicate that hydration reaction of the three kind of expansive agents occurs in the
days. The results here can be supported by the results in Figures 5 and 6, which show that
first 7 days. The results here can be supported by the results in Figures 5 and 6, which
in the first few days, when the Internal RH of UHPC is higher than 80%, the hydration
show that in the first few days, when the Internal RH of UHPC is higher than 80%, the
reaction of the three expansive agents can occur. In addition, the hydration heat of the
hydration reaction of the three expansive agents can occur. In addition, the hydration heat
paste with CaO-based expansive agent increases significantly with the increase of the con-
of the paste with CaO-based expansive agent increases significantly with the increase of
tent of CaO-based expansive agent, while the difference of hydration heat between 4%
the content of CaO-based expansive agent, while the difference of hydration heat between
and 6% medium reactive MgO-based expansive agent is very small. Furthermore, it can
4% and 6% medium reactive MgO-based expansive agent is very small. Furthermore, it
be inferred from the results of the hydration heat that CaO-based expansive agent has the
can be inferred from the results of the hydration heat that CaO-based expansive agent
highest hydration activity in UHPC paste, when compared with the two kinds of MgO-
has the highest hydration activity in UHPC paste, when compared with the two kinds of
based expansive agents. This inference is consistent with the results of the humidity sen-
MgO-based expansive agents. This inference is consistent with the results of the humidity
sitivity of the three kinds of expansive agents.
sensitivity of the three kinds of expansive agents.
Figure
Figure 7.
7. Hydration
Hydrationheat
heatof
ofthe
thepaste
pastewith
withand
andwithout
withoutexpansive
expansiveagent:
agent:(a)(a)highly
highlyreactive MgO-
reactive MgO-
based
based expansive
expansive agent;
agent; (b)
(b) medium reactive MgO-based
medium reactive MgO-based expansive
expansive agent;
agent; and
and (c) (c) CaO-based
CaO-basedexpan-
ex-
pansive agent.
sive agent.
3.5. Micrographs
3.5. Micrographs Analysis
Analysis
Figure 88 shows
Figure shows SEM
SEM photographs
photographs of of three
three kinds
kinds ofof expansive
expansive agents
agents usedused inin this
this
study. A single particle of the MgO-based expansive agent is a porous
study. A single particle of the MgO-based expansive agent is a porous material and is material and is
composed
composed by aggregated magnesia grains [20], which can be clearly observed
aggregated magnesia grains [20], which can be clearly observed in Figure in Figure 8b.
It should
8b. be be
It should noted that
noted in in
that highly
highlyreactive
reactiveMgO-based
MgO-basedexpansive
expansiveagent,
agent, itit is difficult to
to
observe the magnesia
observe magnesia grains due to their small size (see Figure 8a). During During hydration
hydration andand
expansion process
expansion process of
of MgO-based
MgO-based expansive
expansive agent,
agent, the
the pores
pores ofof the
the particle
particle need
need toto be
be
filled by hydration products, and lead to the loss of the expansion efficiency.
filled by hydration products, and lead to the loss of the expansion efficiency. The porosity The porosity
of the
of theMgO-based
MgO-basedexpansive
expansiveagent agentmay
may partly
partly explain
explain why why
thethe expansion
expansion efficiency
efficiency of 6%of
6% highly reactive MgO-based expansive agent is much lower than that of the 3% CaO-
based expansive agent, although at 60–93% RH, the differences of the hydration degree
between highly reactive MgO-based and CaO-based expansive agent are less than 40% at
different ages.
Crystals2022,
Crystals 2022,12,
12,xxFOR
FORPEER
PEERREVIEW
REVIEW 88ofof10
10
highlyreactive
highly reactiveMgO-based
MgO-basedexpansive
expansiveagent
agentisismuch
muchlower
lowerthan
thanthat
thatof
ofthe
the3%
3%CaO-based
CaO-based
expansiveagent,
expansive agent,although
althoughatat60–93%
60–93%RH,
RH,the
thedifferences
differencesof
ofthe
thehydration
hydrationdegree
degreebetween
between
Crystals 2022, 12, 195 8 of 10
highlyreactive
highly reactiveMgO-based
MgO-basedand andCaO-based
CaO-basedexpansive
expansiveagentagentare
areless
lessthan
than40%
40%atatdifferent
different
ages.
ages.
(a)
(a) (b)
(b) (c)
(c)
Figure8.
Figure
Figure 8.8.SEM
SEM images
imagesofof
SEMimages the
ofthe expansive
expansive
the agents:
agents:
expansive (a)(a)
(a)
agents: highly
highly reactive
reactive
highly MgO-based
MgO-based
reactive expansive
expansive
MgO-based agent;
agent;
expansive (b)
(b)
agent;
medium
medium reactive
reactive MgO-based
MgO-based expansive
expansive agent;
agent; and
and (c)
(c) CaO-based
CaO-based expansive
expansive
(b) medium reactive MgO-based expansive agent; and (c) CaO-based expansive agent. agent.
agent.
Figure999shows
Figure showsthe
shows the
the photograph
photograph
photograph ofofof
the the particle
particle
the particle ofhighly
of of highly
highly reactive
reactive
reactive MgO-based
MgO-based
MgO-based atat60%
at 60% 60%
RH.
ItRH.
RH.canItItbecan
can bededuced
deduced
be deduced thathydration
that hydration
that hydration product-Mg(OH)
product-Mg(OH)
product-Mg(OH) 2 forms2 2in forms inthe
theparticle
the particle
forms in particle
of of
highlyof highly
reactive
highly
reactiveMgO-based
MgO-based
reactive MgO-based
expansive expansive
agent from
expansive agent
agent fromits
its rougher
from itssurface
rougher
rougher surfacecompared
compared
surface compared
to Figure totoFigure
6a, Figure
although6a,alt-
6a, alt-
the
hydration
houghthe
hough products
hydrationof
thehydration MgO-based
products
products expansiveexpansive
ofMgO-based
of MgO-based agent canagent
expansive be hardly
agent canbe
can identified
behardly by the SEM
hardlyidentified
identified by
by
photograph
theSEM
the SEMphotographduo to very
photograph duosmall
duo to sizesmall
tovery
very of thesize
small magnesia
sizeof thegrains.
ofthe magnesia
magnesia Unlike MgO-based
grains.
grains. expansive
UnlikeMgO-based
Unlike MgO-based
agent,
expansive
expansive the hydration
agent, theofhydration
agent,the CaO-based
hydration ofofexpansive
CaO-based
CaO-based agent can be easily
expansive
expansive agentobserved
agent canbe
can in photos.
beeasily
easily When
observed
observed in
in
comparing
photos.When
photos. Figures
Whencomparing 1 and 10a,
comparingFigures it can
Figures11and be observed
and10a,10a,ititcan that
canbe the surface
beobserved
observedthat shell
thatthe of clinker
thesurface of
surfaceshell the
shellof of
CaO-based
clinkerof
clinker oftheexpansive
the CaO-based
CaO-based agent is broken
expansive
expansive dueisisto
agent
agent expansive
broken
broken dueto
due hydration
to expansive
expansive products
hydration
hydration at products
60% RH.
products
Furthermore,
at60%
at 60%RH. Figure 10b shows
RH.Furthermore,
Furthermore, Figurethat
Figure the
10bshows
10b showsformation
thatthe
that theof sheet hydration
formation
formation ofsheet
of products,
hydrationwhich
sheethydration is a
products,
products,
typical
whichisfeature
which of Ca(OH)
isaatypical
typical feature2of
feature .ofConsequently,
Ca(OH) the micrographs
Ca(OH)2.2.Consequently,
Consequently, further confirm
themicrographs
the micrographs thatconfirm
further
further CaO-based
confirm that
that
and highly
CaO-based reactive
and MgO-based
highly reactive expansive
MgO-based agents,
expansiveespecially
CaO-based and highly reactive MgO-based expansive agents, especially the CaO-basedagents, the CaO-based
especially the expansive
CaO-based
agent,
expansive
expansive have the hydration
agent,
agent, havethe
have activity
thehydration
hydration atactivity
RH of above
activity RH60%.
atatRH ofabove
of Furthermore,
above the results
60%.Furthermore,
60%. Furthermore, suggest
the
the results
results
that CaO-based
suggestthat
suggest expansive
thatCaO-based
CaO-basedexpansive agent is
expansiveagent a more effective
agentisisaamore method
moreeffective
effectivemethodto compensate
methodto autogenous
tocompensate
compensateautog-autog-
shrinkage
enousshrinkage
enous of UHPC
shrinkage of than
ofUHPC
UHPC MgO-based
thanMgO-based
than expansive
MgO-based agent. agent.
expansive
expansive agent.
(a) (b)
4. Conclusions
In this study, highly reactive MgO-based, medium reactive MgO-based and CaO-
based expansive agents were used to compensate the autogenous shrinkage of UHPC. The
Crystals 2022, 12, 195 9 of 10
4. Conclusions
In this study, highly reactive MgO-based, medium reactive MgO-based and CaO-
based expansive agents were used to compensate the autogenous shrinkage of UHPC. The
effectiveness of three kinds of expansive agents was investigated through the experimental
studies of hydration properties of the expansive agents. The following conclusions can
be drawn:
The internal RH of UHPC decreases very quickly, especially in the first few days. The
RH can reduce to below 80% at 7 d and below 70% at 28 d. Under this condition of rapid
reduction of the RH, the CaO-based expansive agent has the highest expansive efficiency
compared to the two kinds of MgO-based expansive agents.
The CaO-based expansive agent has a high hydration activity at the RH of more than
44%. The hydration activity of the two kinds of MgO-based expansive agents decreased
significantly with the decrease of the RH. Furthermore, the 28 d hydration degree of
medium reactive MgO-based expansive agent does not exceed 5% when the RH decreases
to 60%.
The results indicate that the differences in the expansion efficiency of the three kinds
of expansion agents are closely related to their humidity sensitivity, that is, the expansion
agent with low humidity sensitivity has high expansion efficiency.
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